Method of adhesive bonding

ABSTRACT

Solutions of chlorosulfonated polyethylene or mixtures of sulfonyl chlorides and chlorinated polymers in polymerizable vinyl monomers having a Brookfield viscosity of up to about 1 million form excellent adhesive compositions which cure to high bond strengths. Acrylic monomers are preferred.

REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 551,964, filedFeb. 21, 1975, now abandoned which in turn is a division of applicationSer. No. 357,387, filed May 4, 1974, now U.S. Pat. No. 3,890,407, whichin turn is a continuation-in-part of application Ser. No. 273,353, filedJuly 20, 1972, now abandoned.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 3,591,438 discloses a polymerizable acrylate compositioncomprising an adhesive composition and bonding accelerator, wherein theadhesive composition is a polymerizable acrylate ester monomer and aperoxy polymerization initiator, while the bonding accelerator iscomposed of an amine-aldehyde condensation product and a reducingactivator.

U.S. Pat. No. 3,594,451 describes an elastomeric graft polymer of anamorphous, homogeneously chlorosulfonated polyethylene having gratedthereon polymer chains derived from various vinyl monomers, the weightof the grafted chains being 10-40 weight percent of the chlorosulfonatedpolyethylene.

Grafting of methyl methacrylate on chlorosulfonated polyethylene alsohas been studied by Sato et al., Makromol. Chemie 153, 47 (1972).

U.S. Pat. No. 3,642,750 discloses a sealing composition comprising anacrylic acid ester, a cycloaliphatic monohydric alcohol derived fromdimerized or polymerized cyclopentadiene, and an organic peroxide. Suchmixtures are very stable in the presence of oxygen but harden in theabsence of air or oxygen.

Another sealing system, described in U.S. Pat. No. 3,203,941, is basedon tetraethyleneglycol dimethacrylate, a polyamino compound, and anorganic acid.

The prior art adhesive compositions based on a polymerizable vinylmonomer have some shortcomings; for instance, they frequently areunstable in storage or require long curing times, or do not give strongbonds, or require work in the absence of air. There is a need,therefore, for an adhesive that is storage-stable, can be convenientlyformulated and applied, and gives strong bonds in a short time.

SUMMARY OF THE INVENTION

According to this invention, there is now provided an adhesivecomposition which can be formulated either as a two-part system or as asystem utilizing a primer. In either case, the critical components ofthe adhesive composition of the present invention are a solution of asulfur-bearing composition selected from chlorosulfonated polyethyleneand a mixture of sulfonyl chloride with chlorinated polyethylene in apolymerizable vinyl monomer or a mixture of monomers and apolymerization catalyst.

The sulfur-bearing composition should contain about 25-70 weight percentchlorine and about 3-160 mmoles sulfonyl chloride moiety per 100 gramsof polymer and the polyethylene from which the chlorosulfonated orchlorinated polyethylene is prepared should have a melt index of about4-500. The solution can have a Brookfield viscosity of up to about 1million.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of this invention, the term "polymerization catalyst"means at least one of the following:

(a) a free radical generator,

(b) an initiator

(c) a promoter,

(d) an accelerator.

An initiator is a tertiary amine, for example, N,N-dimethylaniline,N,N-dimethyltoluidine, N,N-diethylaniline, N,N-diisopropyl (p-toluidine)or a guanidine.

A promoter is an organic salt of a transition metal; for example,cobalt, nickel, manganese, or iron naphthenate, copper octoate, ironhexoate, or iron propionate.

An accelerator is an aldehyde-amine condensation product, such as acondensation product of butyraldehyde with a primary amine, forinstance, with aniline or butylamine. In general, the condensationproducts of aliphatic aldehydes with aliphatic or aromatic amines areuseful.

A free radical generator can be an organic peroxide, an organichydroperoxide, a perester, or a peracid.

Suitable polymerizable vinyl monomers for the purpose of this inventioninclude acrylic monomers and mixtures of monomers, such as methylmethacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile,methyl acrylate, ethyl acrylate, butyl methacrylate, cyclohexylmethacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, laurylmethacrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate,2-ethylhexyl acrylate, lauryl acrylate, methacrylic acid, acrylic acid,glycidyl methacrylate, itaconic acid, ethylene glycol and higher-glycolacrylates and methacrylates, acrylamide, and methacrylamide; halogenatedmonomers such as vinylidene chloride, chlorostyrene,2,3-dichloro-1,3-butadiene, and 2-chloro-1,3-butadiene; and styrene andmono- and polyalkylstyrenes, such as methylstyrene, dimethylstyrene,ethylstyrene, or tert-butylstyrene. The preferred monomers are acrylicmonomers, especially lower alkyl acrylates and methacrylates andethylene glycol diacrylate and dimethacrylate.

The choice of the monomer will, of course, depend to some extent on thedesired bond rheology, as well as the solubility of the chlorosulfonatedor chlorinated polyethylene in the monomer. Solutions having aBrookfield viscosity of more than about 1 million cps (ASTM V 490.0500)are impractical to handle. When rigid assemblies having high shearstrength are required, the monomer mixture should have a high glasstransition temperature, for example, using methyl methacrylate of aglass transition temperature of 105° C. For more flexible structures,e.g., where the adhesive layer is intended to contribute to vibrationdampening at room temperature, a glass transition temperature of thecombined copolymer of about -20° C. is preferred.

The chlorosulfonated polyethylene suitable in the process of the presentinvention can be prepared in a manner well known to those skilled in theart by reaction of linear or branched polyethylene and sulfurylchloride, or sulfur dioxide and chlorine. Chlorosulfonated polyethyleneis also available commercially, for example, under the trade nameHypalon®. In practice, the chlorosulfonated polyethylene may also be achlorosulfonated copolymer of ethylene with small proportions ofpropylene or other olefins. Various chlorosulfonated polyethylenes andmethods of their preparation are discussed, for example, in U.S. Pat.No. 2,982,759, which is incorporated herein by reference. Alternatively,sulfonyl chloride and chlorinated polyethylenes of suitable molecularweight can be used. The sulfonyl chlorides can be mono- orpoly-functional and can be C₁ -C₁₂ alkyl sulfonyl chlorides, such asmethane or butane sulfonyl chloride, C₆ -C₂₄ aromatic sulfonyl chloridessuch as benzene or toluene sulfonyl chloride. Some sulfonyl chloridescontaining hetero atoms have also been found to work, such asdiphenylether-4,4'-disulfonyl chloride.

The relative proportions of chlorosulfonated polyethylene andpolymerizable vinyl monomer can vary within a rather broad range. In thecase of acrylic polymers, the practical range is about from 25 to 2000parts by weight of the monomer per 100 parts of chlorosulfonated orchlorinated polyethylene. The preferred range is 50-500 parts by weightof the monomer per 100 parts of polymer, whether chlorosulfonatedpolyethylene or a mixture of sulfonyl chloride and chlorinatedpolyethylene is used.

The adhesive compositions of the present invention require apolymerization catalyst to cause hardening of the composition within apractical time. One or more of the catalysts described in the Summary ofthe Invention can be used, but the following catalysts or catalystcombinations are particularly suitable:

(a) an initiator plus a promoter,

(b) an accelerator,

(c) a free radical generator and an initiator plus a promoter, and

(d) a free radical generator and an accelerator

Free radical generators are well known to those skilled in the art andare described, for example, in "Free Radicals in Solution", C. Walling,J. Wiley & Sons, New York, 1957, and in "The Chemistry of Organic FilmFormers", D. H. Solomon, J. Wiley and Sons, New York, 1967, p. 135 ff.

The preferred free radical generators are organic peroxides andhydroperoxides.

An amine initiator is usually used together with a transition metalcompound as a promoter. Their respective relative weight proportionsshould be about be about 4:1 to 1:1. The preferred proportion is about2:1 by weight of the initiator to the promoter. It is also possible touse an initiator or promoter alone, but the combination is much moreeffective. The preferred initiator is N,N-dimethylaniline, while thepreferred promotor is cobalt naphthenate.

Various aldehydes and amines are suitable for the preparation ofaccelerators useful in the present invention. The aldehydes willpreferably be aliphatic aldehydes having 1-12 carbon atoms. Any primaryaliphatic or aromatic amine having up to about eighteen carbon atoms issuitable. Several useful accelerators are described in the above citedU.S. Pat. No. 3,591,438.

Typical aldehydes include, for example, acetaldehyde, butyraldehyde,propionaldehyde, cyclopentanal, hexanal, cyclohexanal,hydrocinnamaldehydes, heptanal, decanal, and dodecanal. Typical aminesinclude, for example, ethylamine, butylamine, pentylamine,cyclopentylamine, hexylamine, cyclohexylamine, octylamine, decylamine,dodecylamine, hexadecylamine, octadecylamine, aniline, tolyl amines, andxylyl amines. In both the aldehyde and the amine series,various-position isomers are possible.

The proportion of the polymerization catalyst will affect the set timeof the composition. In the absence of the accelerator, a compositioncontaining about 0.2 weight percent of a peroxide is stable for abouttwo weeks. In the absence of a catalyst, a solution of chlorosulfonatedpolyethylene, for example, in a monomer is stable for at least severalmonths under normal storage conditions. In the presence of both a freeradical generator and an accelerator, the maximum bond strength can bereached within about 3-5 minutes at room temperature. It is one of theadvantages of the present system that it cures quickly to a strong bondat room temperature, no aftertreatment being required.

The following concentrations of polymerization catalysts, as weightpercent of the solution of polymer in monomer have been found to bepractical:

free radical generator up to 10%, 0.05-3% being preferred;

accelerator up to 15%, 0.01-1.5% being preferred;

initiator up to 5%; 0.01-1.5% being preferred; and

promotor up to 5%, 0.01-0.75% being preferred.

The adhesive compositions of the present invention can be formulated asa two-part system, wherein one part is a solution of polymer in apolymerizable vinyl monomer. The other part is the polymerizationcatalyst. Alternatively, it can be formulated as a primer system inwhich the polymerization catalyst is the primer and the adhesivesolution is the polymer mixture. Usually, the catalyst will be either anaccelerator or an initiator plus promoter. The curing rates can beincreased by adding a free radical generator to either composition. Ingeneral, at any level of the polymerization catalyst, the rate of bondformation of a system employing an initiator plus promoter is lower thanthe rate of bond formation of a system employing only an accelerator.

The two-part system gives very strong bonds of 2500-3500 psi lap shear.The two-part system using only an accelerator has a very short pot life.If an initiator and a promoter are used instead of an accelerator, thesystem's pot life can be extended. In practice, one or both surfaces tobe joined are coated with the adhesive composition obtained by mixingboth parts, and the surfaces are then placed in contact with each other.

In the primer system, a primer is first applied to one or both surfacesto be joined; then a solution of polymer in a vinyl monomer is appliedto at least one of the surfaces. The solution can optionally contain afree radical generator. The primer is an accelerator, as defined above.

The primer system is operationally more convenient than the two-partsystem, and it gives a good bond strength of about 2500-3500 psi inshear when cured. Furthermore, it gives more rapid development ofload-bearing strength.

The setting times for the two-part system and for the primer system willvary somewhat, depending on the nature of the catalyst, but usually willbe about 5-10 min. for the former and 0.5-5 min. for the latter.

It is very unexpected that the adhesive compositions of the presentinvention have their unique property of setting within a short time togive bonds of high load strength. For example, when the sulfonylchloride groups are excluded from the composition, the cure time isconsiderably longer. However, the role of the sulfonyl chloride orchlorosulfonated polyethylene appears to be more complex than justproviding some of the adhesive material. Solutions of polymers in vinylmonomers in the absence of sulfonyl chloride groups fail to produceadhesive compositions like those of this invention when applied tosubstrates and tested. It is possible, in view of the above-mentionedSato et al. publication and U.S. Pat. No. 3,594,451 that somepolymerization of the monomer on the sulfonyl chloride groups takesplace initially and that this polymerization in some manner alsoinitiates the polymerization of the monomer. However, no scientifictheory or explanation is offered, since the exact mechanism of thispolymerization is not well understood. It is well known, for example,that monomers can be grafted on virtually any polymeric material underproper conditions, but only sulfonyl chloride groups are suitable in theadhesive compositions of this invention.

The instant compositions offer several additional advantages. Thus, theyare used at room temperature, no heat being required either for applyingthe compositions to the substrates or for curing. They can be used onporous surfaces, unlike those prior art adhesives which require theabsence of air and thus cannot be used on surfaces containing air intheir pores. The bonds containing elastomeric polymers such aschlorosulfonated polyethylene are flexible. The instant compositions donot require a careful surface preparation but can be used, for example,on bonderized or oily steel.

Other possible substrates which can be bonded by means of thecompositions of this invention include ordinary steel, etched aluminum,copper, brass, polar polymeric materials, (i.e., those having variousfunctional groups, e.g., polyesters, polyamides, polyurethanes,polyvinyl chloride, etc.), wood, prepainted surfaces, glass and paper.

This invention is now illustrated by the following examples of certainpreferred embodiments thereof, wherein all parts, proportions, andpercentages are by weight unless otherwise indicated.

EXAMPLE 1

To a mixture of acrylic monomers comprising 85 g of methyl methacrylate(containing 50-90 ppm of hydroquinone inhibitor), 15 g of glacialmethacrylic acid (containing 250 ppm of 4-methoxyphenol), and 2 g ofethylene glycol dimethacrylate, there was added 100 g ofchlorosulfonated polyethylene, made from branched polyethylene having amelt index of 100 and containing 43% chlorine and 34 mmoles sulfonylchloride/100 grams of polymer. The mixture was rolled in a jar at roomtemperature until solution of the polymer was complete (24-48 hours).

An adhesive composition was prepared by stirring into 50 g of the abovesolution, in turn, 1.5 g of cumene hydroperoxide and 0.5 g ofN,N-dimethylaniline.

Lap shear bonds were prepared by pressing a small amount of the adhesivecomposition between 1 inch × 3 inch × 0.064 inch grit blasted andperchloroethylene vapor degreased hot rolled steel coupons in a mold sothat a glue line of 0.010 inch × 1 inch × 1 inch was obtained. Thespecimens were stored for 18 hours in a nitrogen atmosphere (optional)and fourteen days in air at room temperature. The specimens were testedin shear at a separation rate of 0.5 inch/minute and failed adhesivelyat 2850 psi (ASTM D-1002-64).

Aluminum "T" peel specimens were prepared by pressing the adhesivecomposition between 1 inch × 10 inch × 0.018 inch etched aluminum stripsso that a glue line thickness of 0.005-0.010 inch was obtained. Thesamples were stored as described above and tested in 180° peel at aseparation speed of 10 inches per minute (ASTM D-1876-61T). The averagepeel strength obtained was 35 pounds per linear inch with mixed adhesiveand cohesive failure.

EXAMPLE 2

A second, shelf-stable adhesive composition was prepared by stirring0.130 g of cumene hydroperoxide into 65.3 g of the chlorosulfonatedpolyethylene/acrylic monomers solution described in Example 1. Lap shearbonds were prepared by applying to steel coupons (treated as describedin Example 1) an accelerator which was a mixture of butyraldehyde andaniline condensation products (sold as DuPont Accelerator 808). Theaccelerator was applied with a cotton swab and then wiped to a thin filmwith a piece of cloth. The adhesive was pressed between the treatedsteel coupons to give a layer 0.005-0.010 inch thick. The following rateof shear strength development was observed:

                  Table I                                                         ______________________________________                                        Time (min.)   Lap Shear Strength (psi)                                        ______________________________________                                         3            1450                                                            10            2030                                                            30            2050                                                            60            2100                                                            ______________________________________                                    

EXAMPLES 3-8

Polymer solutions containing the following were prepared as described inExample 1:

100 g chlorosulfonated polyethylene (the polymer described in Example 1)and the acrylic monomer listed for each example in the table. Adhesivecompositions were prepared as follows: to 25 g of each solution wereadded 0.125 g cumene hydroperoxide, 0.06 g N,N-dimethylaniline, and 0.04g cobalt napthenate. Lap shear and T-peel test assemblies were thenprepared as described in Example 1. The test results are shown in thetable, below:

                  Table II                                                        ______________________________________                                        Exam-                    Lap Shear  T-Peel                                    ple    Monomer Compositions                                                                            (psi)      (pli)                                     ______________________________________                                        3      Methyl methacrylate                                                           100               1100       *                                         4      Ethyl methacrylate                                                            100               1725       *                                         5      Methacrylic acid 10                                                           Methyl methacrylate                                                           90                2650       19                                        6      N-butyl methacrylate                                                          90                                                                            Methacrylic acid 10                                                                             2500       15                                        7      Methacrylic acid 10                                                           Methyl methacrylate                                                           45                                                                            N-butyl methacrylate                                                          45                2850       5.0                                       8      Methacrylic acid 10                                                           Methyl methacrylate                                                           45                                                                            2-Ethylhexylmethac-                                                           rylate 45         2780       22                                        ______________________________________                                         *Not tested                                                              

EXAMPLES 9-13

Adhesive compositions were prepared as described below and the peaktemperature of the exothermic polymerization was measured, as was thetime to achieve that temperature. Polymer solutions containing thefollowing were prepared as described in Example 1:

40 g of chlorosulfonated polyethylene made from polyethylenecharacterized in columns 2 and 3 of Table III below, 145 g methylmethacrylate, 15 g methacrylic acid, and 3.2 g ethylene glycoldimethacrylate. Adhesive compositions were prepared by adding 0.3 g ofthe butyraldehydeaniline condensation product described in Example 2 to25 g of the polymer solution. The results in Table III show that allthese compositions are suitable as rapid setting adhesives.

                                      Table III                                   __________________________________________________________________________                    Chlorosulfonated                                                          Melt                                                                              Polyethylene  Peak                                            Example                                                                            Polyethylene                                                                         Index                                                                             % Cl                                                                              SO.sub.2 Cl*                                                                       Time Temperature                                     __________________________________________________________________________     9   Branched                                                                             10  29  44   20 min.                                                                             97.5                                                                            ° C.                                  10   Branched                                                                             100 43  34   32 min.                                                                             77                                                                              ° C.                                  11   Linear 12-14                                                                             35  31   29 min.                                                                            104                                                                              ° C.                                  12   Linear 5.0 35  31   28 min.                                                                            105                                                                              ° C.                                  13   Linear 14-15                                                                             43  31   18.5 min.                                                                          105                                                                              ° C                                   __________________________________________________________________________     *mmoles/100 g polymer                                                    

EXAMPLE 14

Steel coupons were bonded by the primer technique of Example 2 using anadhesive composition based on methyl methacrylate, methacrylic acid,ethylene glycol dimethacrylate, and chlorosulfonated polyethylene, as inExample 1. The solution contained no polymerization catalyst. Thefollowing lap shear strengths were recorded as a function of time.

                  TABLE IV                                                        ______________________________________                                        Bond Age     Lap Shear Strength                                               Minutes      (psi)                                                            ______________________________________                                         20               1-2                                                         60                80                                                          120               600                                                         240              1040                                                         300              1520                                                         24       hours   2300                                                         ______________________________________                                    

This example shows that in the absence of a catalyst the adhesivecomposition requires several hours to cure completely but gives a bondof high strength.

EXAMPLES 15 and 16

The process of Example 1 was repeated, except that no hydroperoxide wasadded to the chlorosulfonated polyethylene solution in monomers. Theeffectiveness of an initiator alone and of a combination of an initiatorand a promotor were compared by measuring the respective lap shearstrengths, shown in Table V.

                  Table V                                                         ______________________________________                                                                         Lap Shear                                                                     Strength                                     Example Initiator.sup.1                                                                            Promoter.sup.1                                                                            (psi).sup.2                                  ______________________________________                                        15      1% N,N-      --          1400                                                 dimethylaniline                                                       16      1% N,N-      0.4% Cobalt 2100                                                 dimethylaniline                                                                            Naphthenate                                              ______________________________________                                         .sup.1 Based on the weight of chlorosulfonated polyethylene solution in       acrylic monomers, as described in the first paragraph of Example 1.           .sup.2 Bonds aged four days at room temperature.                         

This example shows that although good bonds can be obtained usinginitiator alone, better bonds are obtained if a promoter is also used.

EXAMPLE 17

An adhesive base solution was prepared by dissolving 100 g of 44.7%chlorinated low-density polyethylene, the polyethylene sold as "Alathon"3034 by E. I. du Pont de Nemours and Co., Inc., in a mixture of methylmethacrylate (88 g), methacrylic acid (10 g) and ethylene dimethacrylate(2 g). To samples of the solution were added 1 part per 100 (based ontotal solution) cumene hydroperoxide and 30 mmoles sulfonyl chloride/100g polymer of the sulfonyl chlorides indicated in the table below. Lapshear adhesive specimens were prepared by applying each solution to 1inch by 3 inch steel strips which were coated with a light film of acondensation product of butyraldehyde and aniline sold as "Accelerator"808 by E. I. du Pont de Nemours and Co., Inc., and affixing a similarlytreated strip such that a one-square-inch overlap resulted. Theassemblies were pressed together in molds which gave uniform bondthicknesses of 0.007--0.010 in.

The specimens were tested one hour after assembly in an Instronapparatus with a separation rate of 0.5 inches per minute (ASTMD-1876-61T). The following lap shear strengths were recorded as theaverage of four specimens.

                  Table VI                                                        ______________________________________                                                       1-Hour Lap Shear                                               Sulfonyl Chloride                                                                            Strength                                                       ______________________________________                                        None            160 psi                                                       p-Toluenesulfonyl                                                             chloride       2100 psi                                                       Methanesulfonyl                                                               chloride       2030 psi                                                       ______________________________________                                    

EXAMPLE 18

An adhesive solution contained 25 wt. percent chlorinated (35 wt. %)high density polyethylene, 7.4 wt. percent methacrylic acid, 2 wt.percent ethylene dimethacrylate and 65.6 wt. percent methylmethacrylate. To the solution was added 1 part per 100 cumenehydroperoxide based on total solution and 67 mmoles of p-toluenesulfonylchloride per 100 g polymer. Lap shear samples were prepared and testedas described in Example 17. The one-hour lap shear strength was 860 psi.A control sample containing no p-toluene-sulfonyl chloride had 0 lapshear strength.

EXAMPLE 19

To an adhesive base solution containing 39.6 wt. percent chlorinated(41.4%) low-density polyethylene, 52 wt. percent methyl methacrylate,7.4 wt. percent methacrylic acid and 1 wt. percent ethylenedimethacrylate were added the various amounts of diphenylether-4,4-disulfonyl chloride indicated in the table. Test specimenswere prepared and tested as in Example 17 and as shown in the table.

                  Table VII                                                       ______________________________________                                        Mmoles Sulfonyl                                                               Chloride/100 gm.                                                              Polymer       0        1      10   75    150                                  ______________________________________                                        Lap Shear Strength                                                            Condition 1    15    psi    245  210  95   155                                Condition 2   220          2175 2385 not   →                                                                tested                                   Condition 3   nil          nil  1020 830   435                                ______________________________________                                    

Condition

1. No cumene hydroperoxide added; duplicate samples.

2. 1 part per 100 cumene hydroperoxide added; same testing as forCondition 1.

3. 1 part per 100 cumene hydroperoxide added. A thin film of thebutyraldehyde-aniline adduct of Example 17 was applied to each of twosteel strips. The strips were affixed in the jaws of the testingapparatus such that they overlapped one inch. The adhesive solution wasapplied between the strips, which were then held firmly together bymeans of two 3/4 inch paper clips. (A bond line of 1-2 mils resulted.)The samples were tested four min. after assembly.

In the following composition claims, the term "consisting essentiallyof" means that, in addition to the recited components, the compositionmay also contain other components that do not adversely affect theoperability of the composition for its intended purpose.

We claim:
 1. A method of bonding two surfaces to each other, said method comprising applying to at least one of the surfaces to be joined an adhesive composition consisting essentially of a solution of a sulfur-bearing composition selected from chlorosulfonated polyethylene and a mixture of sulfonyl chloride with chlorinated polyethylene in a polymerizable vinyl monomer and at least one polymerization catalyst selected from the group consisting of an accelerator, an initiator, a promoter, and a free radical generator; the sulfur-bearing composition containing about 25-70 wt. percent chlorine and about 0.1-5 weight percent sulfur and being made from polyethylene having a melt index of about 4-500; said solution having a Brookfield viscosity of up to about 1 million; and then bringing the surfaces sufficiently close together that the adhesive composition fills the gap between the surfaces to create a bond that can be characterized by at least one of the following: the setting time is less than about 10 minutes, the T-peel strength is greater than about 5 pli, the lap shear strength on prepared surfaces is greater than about 2500 psi, and the bond strength on oily surfaces is not significantly adversely affected by the presence of the oil.
 2. A method of claim 1 wherein the polymerization catalyst is an organic peroxide or hydroperoxide, and the vinyl monomer is an acrylic monomer.
 3. A method of bonding two surfaces to each other, said method comprising applying to at least one of the surfaces to be joined an accelerator; next, applying to at least one of said surfaces an adhesive composition consisting essentially of a solution of sulfur-bearing composition selected from chlorosulfonated polyethylene and a mixture of chlorinated polyethylene and sulfonyl chloride in a polymerizable vinyl monomer and containing at least one member of the group consisting of free radical generators, initiators, and promoters; the sulfur-bearing composition containing about 25-70 wt. percent chlorine and about 3-160 mmoles sulfonyl chloride moiety per 100 g of polymer and being made from polyethylene having a melt index of about 4-500; said solution having a Brookfield viscosity of up to about 1 million; and then bringing the surfaces sufficiently close together that the adhesive composition fills the gap between the surfaces to create a bond that can be characterized by at least one of the following: the setting time is less than about 10 minutes, the T-peel strength is greater than about 5 pli, the lap shear strength on prepared surfaces is greater than about 2500 psi, and the bond strength on oily surfaces is not significantly adversely affected by the presence of the oil.
 4. A method of claim 3 wherein the adhesive composition contains an organic peroxide or hydroperoxide free radical generator and the vinyl monomer is an acrylic monomer.
 5. A method of claim 3 wherein the accelerator is a primary amine-aldehyde condensation product. 